Manufacture of artificial materials



J. H. ROONEY ET AL MANUFACTUURE OF ARTIFICIAL MATERIALS ,Original Filed Nov. 27, 1937 JAMES H- RODNEY PHILIP KHAWTIN STEPHEN R-CHAVLIN mvfwroxs 7 man Patented Aug.V 18, 1,942

A azsam Y MANUFACTURE or ARTIFICIAL MATERIALS James Henry Rooney and Philip Richard`Hawtin, Spenden, near Derby, and `Stephen Roy Chaplin,

Leicester, England,

assixnors to Celanese Corporation of America, a corporation oi' Delaware Original application November 27, 1937, Serial No. 176,846. Divided and this application June 27, 1940, Serial No. 342,636. In Great Britain December 4, 1936 1 claim. (ci. 1st-15) This invention relates to themanufacture of films, foils and like products by the evaporative method, and provides apparatus for introducing colouring agents or other desired constituents into suchV products during their formation. This application is a division of our application S. No. 176,846, filed November 27, 1937,

I'he manufacture of films, foils and like products by the evaporative method is commonly carried out by extruding a suitable film-forming dope, for example a solution of cellulose acetate in acetone or other volatile solvent, on to a travelling support, e. g. an endless metal band or drum, and effecting evaporation lof the bulk of the volatile solvent during the travel of the extruded material from the extrusion point toa point at which the product is stripped from the support. Coloured films or foils can be obtained either by introducing suitable colouring agents into thev composition to be extruded or by subjecting the finished products to processes analogous to the dyeing of textile materials. Both l these methods, however, present disadvantages.

The rst method does not enable the film-forming apparatus to` be turned over quickly from the production of lms vof one colour to the producoperation. It is the primary object of the present invention to provide apparatus for obtaining coloured lms, foils and like materials by the evaporative method which is free from these disadvantages. u y

According to the invention of application. S. No. 176,846 referred to above, a colouring agent or other desired constituent of the product is introduced by applying a solution of said constituent to the partly dried layer of dope, preferably by flowing the liquid on to thesurface thereof. The liquid should be adapted to spread over the surface of the product to the desired extent and should preferably be removed from said surface at least partly by evaporation, for example partly by evaporationV and partly by absorption, during the travel of the product t composition of the liquid, that the bulk of the volatile constituents such as acetone and alcohol is evaporated by the time the foil reaches the point at which it is stripped from the band. The plasticiser and a certain proportion of the volatile constituents are absorbed into the foil. Among suitable colouring agents are the basic dyes, e. g. methylene blue or malachite green, and water insoluble dyes of the kind used for dyeing cellulose acetate 4textile materials, e. g. 1-4 di(methylamino) anthraquinone, and 4nitro-2 methoxy benzene azo dimethyl aniline. The proportion of plasticiser used should not be sumciently great to have an adverse effect on the tenacity of the products. 'It is indeed not impossible to dispense with the plasticiser, but in that case it is less easy to obtain even colouration owing to the greater mobility of the colouring liquid. u,

A suitable medium for the introduction of the dye into a film or foil during the production by tion of films of another colour, and the second method `introduces an extra and relatively slow y the evaporative method from a dope comprising cellulose acetate dissolved in acetone can be made by dissolving in a -60/60-40% mixture of acetone and alcohol 10-30% of its weight of dimethyl phthalate.

from the extrusion point to the point at which it is stripped from the supporting surface. Thus, coloured foils of cellulose acetate can readily be produced by extruding a solutionl of cellulose acetate in acetone on to an endless nickel band passing through a warm atmosphere and applying to the surface ofthe foil just beyond the extrusion point a solution of a suitable dye in a liquid consisting Vsubstantially of acetone, ethyl ,A suitable device for applying the colouring liquid comprises a reservoir for said liquid7 having an adjustable aperture, a wick or curtain of porous material for conveying the liquid from said reservoir Vto the surface of the film, said wick extending downwardly from the interior of said reservoir through said aperture, means for varying the size of said aperture so as to control the" amount of liquid passing through said curtain to the pro-duct and means for micrometrically adjusting the height of the lower edge of said'curtain above the surface of the product.

A preferred f orm of apparatus according to the invention is shown by way of example in the accompanying drawing wherein Fig. 1 represents diagrammatically the general layout of the apparatus:

Fig. 2 is a detail view in elevation of the liquidsupplying apparatus seen from behind;

Fig. 3 is a detail view in elevation of the liquidsupplying apparatus, seen from one side of the film-forming band, and

Fig. 4 is a part sectional elevation taken along alcohol or a mixture of the two, and containthe line--l 0f Fis. 2.

Referring to'Fig. 1 the endless nlm-forming band I which is composed of nickel or other suitable material is driven by means of the drum II and passes round the idler-drum I2. The band passes in turnthe extrusion device I3 from which a film-forming solution is extruded on to the band, and the liquid-supplying device I4 by means of which the colouring or other desired treating liquid is applied to the freshly extruded film. Heating elements (not shown) are provided for warming the atmosphere through which the nlm-forming band passes. Stripping means, also not shown, vare provided for removing the dried illm from the band.

Referring now to Figs. 2, 3 and 4, the trough I4 is of V-shaped section and has'a fixed side I5 and fixed ends I8 carried .by brackets I1 -which in turn are carried by micrometer screws I8 resting upon fixed brackets I9.

The fixed side I is provided near each end with a lug on which is pivotally mounted a rod 2I which engages the undersideof the fixed rail 22 and is supported by the bolt 24 depending from the lug 25, the whole forming a exlble mounting which prevents rocking of the trough about the micrometer screws I8.

The. other side 26 of the trough is pivotally mounted on a bolt 21 running through the fixed end members of the trough. An'extension 28 ofthe side 26 is adapted to function as a crank to move the side about its pivot 21, so varying the size of the aperture 28a between the two sides of the trough. Between a pair of lugs 29 on the extension 28 is pivotally mounted a nut 30. A differential screw 3l runs through this nut and through a nut 32 pivotally mounted on lugs 33 forming part of a bridge-piece 34 which is bolted to the end members of the trough. Thus, by turning the knurled head 35 of the micrometer screw 3I the size of the aperture 28a can be adjusted within fine limits.

A liquid distributing curtain 31 comprising a foraminous base wound round with layers of flannel or other suitable absorbent material is clamped by means of the micrometer screw 3l between the fixed and movable sides of the trough so as vto ll the space 28a. This curtain extends downwardly towards the lmfforming band and upwardly into the trough, so allowing the liquid 38 within the trough to flow slowly towards the film-forming band I0. Liquid is supplied to the trough by the drip pipe 39 and an overflow pipe 40 is provided.

In operation, the micrometer screws I8 are rst adjusted to bring the curtain 31 into contact with the freshly extruded layer of film 4I and the adjustment is then altered very slightly so as to bring the curtain itself but not the stream of liquid oozing therefrom out of contact with the layer of film.

Whenit is desired to produce uniformly coloured films, the wick or curtain should extend across the whole surface of the band.y `The invention is not, however, limited to the production of uniformly coloured films. Local colouration can be effected by suitable adaptations of the apparatus. Thus, for example, two or morel devices of the kind described, each extending over a part only of the width of the foil, can be employed. These may be in line or in staggered relationship.

As indicated above the process and apparatus of the invention can be used for other purposes besides the application of colouring agents to films, foils and like products, for example to apply effect materials and/or to introduce plasticisers and non-inflammators'.

The invention has been described with particular reference to the manufacture of foils of cellulose acetate since this is one of its most important applications. The apparatus of the in- .vention is, however, quite generally applicable to the production of films, foils, ribbons and like materials by the evaporative method, and particularly to the production 'of such materials from-compositions comprising derivatives of cellulose, for example organic esters such as cellulose formate, butyrate and propionate, esters containing inorganic acidyl radicles such as cellulose ultrate, cellulose nitroacetate, cellulose nitrate acetate propionate, ethers such as methyl, ethyl and benzyl cellulose and ether-esters such as ethyl cellulose acetate and Oxy-ethyl cellulose acetate.

Having described our invention, what we desire to secure by Letters Patent is:

A device for use in introducing coloring agents or other desired constituents into films, foils and like products during their production by the evaporation of a volatile solvent from a layer of dope on a travelling support, said device comprising a reservoir for a liquid containing a coloring agent or other constituent, said reservoir including a trough having xed ends, a xed inclined side and a side pivotally mounted so that its lower edge can swing towards or away from the lower edge of the fixed side, a wick clamped between the lower edges of the two sides so as to close the aperture formed by said two sides, means embodying a micrometer screw for adjusting the position of the pivotally mounted side to control the amount of liquid passing through said wick and means for micrometrically adjusting the height of the lower edge of said wick-abov the surface of the product.

JAMES HENRY ROONEY. PHILIP RICHARD HAWTIN. STEPHEN ROY CHAPLIN. 

